CN105032348B - A kind of redox graphene/nano zirconium dioxide composite adsorption dephosphorization agent and preparation method - Google Patents
A kind of redox graphene/nano zirconium dioxide composite adsorption dephosphorization agent and preparation method Download PDFInfo
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Abstract
The invention discloses a kind of redox graphene/nano zirconium dioxide composite adsorption dephosphorization agent and preparation method, and it is made up of a certain proportion of graphene oxide, nano zirconium dioxide, step：A. graphene oxide is prepared with graphite powder：Weigh graphite powder to be placed in dry beaker, add the concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide, add potassium permanganate, hydrogen peroxide, resulting solution through centrifugation, watery hydrochloric acid washing, dry after graphene oxide solid powder；B. prepared by redox graphene/nanometer titanium dioxide zirconium composite material：By the graphene oxide ultrasonic disperse of preparation in deionized water, nano zirconium dioxide is added, transfer suspension reacts into water heating kettle, and the solid of acquisition is washed with deionized, and obtained product is redox graphene/nanometer titanium dioxide zirconium composite material；C. redox graphene/nanometer titanium dioxide zirconium composite material Phosphate Sorption.Big with adsorption capacity, adsorption rate is fast, being capable of circulating repetition utilization.
Description
Technical field
The invention belongs to inorganic nano composite material technical field, is more particularly to a kind of redox graphene/nanometer
Zirconium dioxide composite adsorption dephosphorization agent, also relate to a kind of redox graphene/nano zirconium dioxide composite adsorption dephosphorization
The preparation method of agent, suitable for effluent sewage dephosphorization field of purification.
Background technology
Increasingly strengthen with the fast development and mankind's activity of economy, a large amount of nitrogenous, phosphorus nutrition material sanitary sewages,
Industry and agricultural effluent are drained into rivers and lakes, beyond the self-purification capacity of water body, so as to cause body eutrophication increasingly
Seriously.Body eutrophication can cause water plant amount reproduction, cause Dissolved Oxygen in Water to decline, so as to cause water quality deterioration.
Water quality deterioration can destroy aquatic ecosystem balance, cause the consequences such as the mortality of aquatile.Numerous studies analysis shows, phosphorus
It is the limitation sex factor of algal grown, therefore reduces Phosphorus From Wastewater concentration, for improves existing sewage disposal plant effluent water quality, disappearing
Except lake eutrophication, improvement water body environment are significant.
The waste water dephosphorization method used both at home and abroad at present mainly includes：Chemical precipitation method, absorption method, bioanalysis, membrane technology
Method.Chemical dephosphorization method is simple to operate, and phosphor-removing effect is good, but cost is costly, and sludge output is big and easily causes secondary pollution.Biology
Method dephosphorization is affected by the external environment larger, and the change of such as temperature, pH, dissolved oxygen can all influence the efficiency of bioanalysis dephosphorization, because
This, bioanalysis dephosphorization process operation stability is poor, is unfavorable for ensureing the stabilization of effluent quality.Membrane technology dephosphorization method dephosphorization efficiency
Height, secondary pollution is small, but cost and technical requirements are higher.
Comparatively, it is excellent to have that technique is simple, floor space is small, operating cost is low, secondary pollution is few etc. for adsorption and dephosphorization method
Point.But the key of absorption method is to select suitable adsorbent, and major requirement has（1）Adsorption capacity is big and property is stable；（2）Choosing
Selecting property is good；（3）Adsorption rate is fast；（4）Resist other ion interference abilities strong.
Nano zirconium dioxide has layered mesoporous structure, and specific surface area is big, can ensure enough activated adoption sites, add
Itself is nontoxic, chemical stability is good, therefore it receives much concern in recent years as phosphorus adsorbent.But zirconium dioxide is heavy
Drop property is poor, it is difficult to reclaims, single use goes dephosphorization to cause secondary pollution to water body.Graphene oxide composite material has very high
Specific surface area, stability is preferable, and corrosion-resistant, resistance to oxidation, high temperature resistant low temperature, it is nontoxic, secondary pollution will not be caused, its surface
The functional groups such as existing carbonyl, hydroxyl, epoxy radicals provide metal active adsorption site, easily modified, but itself dephosphorization
It is less efficient.
The present invention is combined nano zirconium dioxide with graphene oxide composite material, nano zirconium dioxide is uniformly dispersed in oxygen
Graphite alkene surface and strong bonded, it is integrated the advantages of both active set nano zirconium dioxide and graphene oxide, improves
The absorption property and practical application characteristic of nano zirconium dioxide.
The content of the invention
The purpose of the present invention is to be the provision of a kind of redox graphene/nano zirconium dioxide composite adsorption dephosphorization
Agent, the adsorption and dephosphorization agent can not only improve nanometer two using the synergy of redox graphene and nano zirconium dioxide
The performance of zirconium oxide Phosphate Sorption, and the premium properties of redox graphene can be utilized.The adsorption and dephosphorization agent has absorption
Capacity is big, and property is stable, and adsorption rate is fast, being capable of circulating repetition the advantages that utilizing.
Another object of the present invention is to be the provision of a kind of redox graphene/nano zirconium dioxide composite adsorption
The preparation method of dephosphorization agent.This method is simple and easy, easy to operate, and yield is high, and the wasting of resources is few, and to instrument and equipment requirement
It is low, use reagent green safe, non-secondary pollution.
In order to realize above-mentioned purpose, the present invention uses following technical measures：
A kind of redox graphene/nano zirconium dioxide composite adsorption dephosphorization agent, it is made up of following raw material：
Parts by weight of raw materials
Graphene oxide 1-40
Nano zirconium dioxide 1-30.
A kind of redox graphene/nano zirconium dioxide composite adsorption dephosphorization agent, it by following parts by weight raw material system
Into（Preferred scope）：
Parts by weight of raw materials
Graphene oxide 2-30
Nano zirconium dioxide 2-20.
A kind of redox graphene/nano zirconium dioxide composite adsorption dephosphorization agent, it by following parts by weight raw material system
Into（Preferable scope）：
Parts by weight of raw materials
Graphene oxide 3-30
Nano zirconium dioxide 3-15.
A kind of redox graphene/nano zirconium dioxide composite adsorption dephosphorization agent, it by following parts by weight raw material system
Into（Best scope）：
Parts by weight of raw materials
Graphene oxide 4-12
Nano zirconium dioxide 4-10.
A kind of redox graphene/nano zirconium dioxide composite adsorption dephosphorization agent, it by following parts by weight raw material system
Into（Optimum value）：
Parts by weight of raw materials
Graphene oxide 10
Nano zirconium dioxide 2.
A kind of preparation method of redox graphene/nano zirconium dioxide composite adsorption dephosphorization agent, its step are：
A. graphene oxide is prepared with graphite powder（Improved Hummers methods, reference Guerrero-Contreras J,
Caballero-Briones F. Graphene oxide powders with different oxidation degree,
prepared by synthesis variations of the Hummers method[J]. Materials
Chemistry and Physics, 2015,153：209-220.）：The graphite powder for weighing certain part by weight is placed in dry beaker
It is interior, the concentrated sulfuric acids of 20-40 mL 98% are added, in 78-82 DEG C of stirred in water bath, are slowly added to 5-10 g potassium peroxydisulfates and 5- successively
10 g phosphorus pentoxides, after persistently stirring 4-6h, it is cooled to room temperature（It is 20-25 DEG C, same as below）, it is dilute to add deionized water
Release, stand overnight.With 0.2 micrometer Millipore filter membrane by powder filter, and it is washed with deionized, until after solution is changed into neutrality,
Powder is in 68-72 DEG C of drying.The powder being dried to obtain is transferred in beaker, the addition concentrated sulfuric acids of 200-300 mL 98%, and in
Stirred under condition of ice bath, be hereafter slowly added to 20-50 g potassium permanganate, after 30-35 DEG C of stirred in water bath 1-3h, use deionization
Water dilutes, lasting stirring, adds 30-50 mL 30% hydrogen peroxide.Solution is centrifuged, and washed with watery hydrochloric acid, with
Remove sulfate ion, detected with barium nitrate solution, completely remove sulfate ion after be washed with deionized until
Washing lotion is neutrality, and obtained product is dried at 68-72 DEG C, that is, obtains graphene oxide solid powder.
B. the preparation of redox graphene/nanometer titanium dioxide zirconium composite material：The graphene oxide being prepared is surpassed
Sound is scattered in deionized water, prepares 1 g/L graphene oxide dispersion.The 0.01-1 g commercialization through pre-treatment is received
Rice zirconium dioxide is added to appropriate volume（5-100 mL）1g/L graphene oxide solutions in, after stirring 1-3h, transfer is outstanding
Supernatant liquid reacts 5-6 h into water heating kettle under 148-152 DEG C of environment.The solid of acquisition is washed with deionized, and in
11-13h is dried under conditions of 58-62 DEG C in vacuum drying chamber to be dried, the product being dried to obtain is oxygen reduction fossil
Black alkene/nanometer titanium dioxide zirconium composite material.
C. redox graphene/nanometer titanium dioxide zirconium composite material Phosphate Sorption：By reduction-oxidation graphite obtained above
Alkene/nanometer titanium dioxide zirconium powder, weigh 0.1-1g be added to certain volume concentration be 1-15 mg/L solution containing phosphate in, fill
Divide and mix, constant-temperature table concussion 22-26h, make to reach adsorption equilibrium.After adsorption equilibrium, composite and phosphorus mixed liquor are centrifuged
Filtering, filtrate calculate adsorbance using molybdenum blue colorimetric method measure balance phosphorus concentration.
Before described graphene oxide and commercialization nano zirconium dioxide is compound, at nano zirconium dioxide first 550 DEG C of calcinings
1-3h is managed to remove the impurity on surface.
Described redox graphene/nano zirconium dioxide method for synthesizing composite material is one step hydro thermal method.Its feature
The reaction 5-6 h under 150 DEG C of environment are that, and carry out 12h dryings in vacuum drying chamber under conditions of 60 DEG C.Preparing
During graphene oxide be partially reduced, turn into redox graphene.
Adding for other reagents is not needed in described redox graphene/nanometer titanium dioxide zirconium composite material building-up process
Enter.
The present invention compared with prior art, has advantages below and effect：
（1）The inventive method, as carrier, can effectively be loaded nano zirconium dioxide particle, prevented using graphene oxide
Only its reunion in water, significantly improve the adsorption capacity and stability of nano zirconium dioxide.
（2）The present invention prepares the one step hydro thermal method of redox graphene/nanometer titanium dioxide zirconium composite material without using it
Its chemical reagent, it is green, simple and easy.
（3）The oxy radical of surface of graphene oxide obtains redox graphene in preparation process after partial reduction,
Its surface potential is improved, compared to graphene oxide, has been strengthened for the adsorption capacity of anionic pollutant in water.
（4）The redox graphene that the present invention is prepared/nano zirconium dioxide composite dephosphorization adsorbent and nanometer two
Zirconium oxide, which is compared, has bigger adsorbance, higher adsorption efficiency, and can recycle.
Brief description of the drawings
Fig. 1 is a kind of scanning of redox graphene/nanometer titanium dioxide zirconium composite material adsorption and dephosphorization agent（SEM）And thoroughly
Penetrate electron microscopic picture（TEM）Schematic diagram.
Wherein (a) and (b) are respectively the scanning electron microscope (SEM) photograph of graphene oxide and redox graphene, and (c) is oxygen reduction
Graphite alkene/nanometer titanium dioxide zirconium composite material scanning electron microscope (SEM) photograph, (d) are that redox graphene/nano zirconium dioxide is compound
Material high-resolution-ration transmission electric-lens figure.
Fig. 2 is a kind of X-ray energy spectrogram of redox graphene/nanometer titanium dioxide zirconium composite material（EDX）Schematic diagram.
Fig. 3 is a kind of X-ray diffractogram of redox graphene/nanometer titanium dioxide zirconium composite material adsorption and dephosphorization agent
（XRD）Schematic diagram.
Wherein (a) and (b) is respectively graphene oxide and redox graphene XRD spectrum, and (c) is oxygen reduction fossil
The XRD spectrum of black alkene/nano zirconium dioxide composite material adsorbent.
Fig. 4 is that a kind of redox graphene/infared spectrum of the nanometer titanium dioxide zirconium composite material before and after Phosphate Sorption shows
It is intended to.
Wherein (a) is graphene oxide infared spectrum, and (b) and (c) is respectively redox graphene/nanometer titanium dioxide
Infared spectrum of the zirconium composite material before and after Phosphate Sorption.
Embodiment
Embodiment 1：
A kind of redox graphene/nano zirconium dioxide composite adsorption dephosphorization agent, it by following parts by weight raw material system
Into：
Parts by weight of raw materials
Graphene oxide 2
Nano zirconium dioxide 2.
A kind of preparation method of redox graphene/nano zirconium dioxide composite adsorption dephosphorization agent, its step are：
A. graphene oxide is prepared with graphite powder：Weigh 6g graphite powders to be placed in dry beaker, then add 24mL
98% concentrated sulfuric acid, in 80 DEG C of stirred in water bath, 5g potassium peroxydisulfates and 5g phosphorus pentoxides are then slowly added to successively, lasting stirring
After 5h, room temperature is cooled to, 1 L deionized waters is added and is diluted, stand overnight.With 0.2 micrometer Millipore filter membrane by powder filter,
It is washed with deionized three to five times, until solution is changed into neutral, powder is dried under the conditions of 70 DEG C.The powder being dried to obtain turns
Move in beaker, the addition concentrated sulfuric acids of 240mL 98%, agitated liquid under condition of ice bath, 30g potassium permanganate is slowly added to, at 35 DEG C
After stirred in water bath 2h, 500mL deionized waters are slowly added to, the deionized water that 1.4 L are persistently added after stirring 2h is diluted,
It is eventually adding 40 mL hydrogen peroxide (30%).Solution is centrifuged, first washed with watery hydrochloric acid, to remove sulfate ion, and
Detected with barium nitrate solution, treat to be washed with deionized after removing sulfate ion completely up to washing lotion is neutral, general
Obtained product is dried at 70 DEG C, that is, obtains graphene oxide solid powder.
B. the preparation of redox graphene/nanometer titanium dioxide zirconium composite material：The graphene oxide being prepared is surpassed
Sound is scattered in deionized water, prepares 1 g/L graphene oxide dispersion.0.01 g nano zirconium dioxides are added to 10
In mL 1 g/L graphene oxide solutions, after stirring 2 h, transfer suspension makes it at 150 DEG C into 100 mL water heating kettles
Lower reaction 5-6 h.The solid of acquisition, is washed with deionized 3-4 times, and is dried under conditions of 60 DEG C in vacuum drying chamber
12h is dried, and the product being dried to obtain is redox graphene/nanometer titanium dioxide zirconium composite material.
Embodiment 2：
A kind of redox graphene/nano zirconium dioxide composite adsorption dephosphorization agent, it by following parts by weight raw material system
Into：
Parts by weight of raw materials
Graphene oxide 3
Nano zirconium dioxide 4.
A kind of preparation method of redox graphene/nano zirconium dioxide composite adsorption dephosphorization agent, its step are：
A. graphene oxide preparation method is same as Example 1.
B. the preparation of redox graphene/nanometer titanium dioxide zirconium composite material：The graphite oxide being prepared is dilute super
Sound is scattered in deionized water, prepares 1 g/L graphene oxide dispersion.0.02 g nano zirconium dioxides are added to 15
In mL 1 g/L graphene oxide solutions, after stirring 2 h, transfer suspension makes it at 150 DEG C into 100 mL water heating kettles
Lower reaction 5-6 h.The solid of acquisition, is washed with deionized 3-4 times, and is dried under conditions of 60 DEG C in vacuum drying chamber
12h is dried, and the product being dried to obtain is redox graphene/nanometer titanium dioxide zirconium composite material.
Embodiment 3：
A kind of redox graphene/nano zirconium dioxide composite adsorption dephosphorization agent, it by following parts by weight raw material system
Into：
Parts by weight of raw materials
Graphene oxide 5
Nano zirconium dioxide 6.
A kind of preparation method of redox graphene/nano zirconium dioxide composite adsorption dephosphorization agent, its step are：
A. graphene oxide preparation method is same as Example 1.
B. the preparation of redox graphene/nanometer titanium dioxide zirconium composite material：The graphite oxide being prepared is dilute super
Sound is scattered in deionized water, prepares 1 g/L graphene oxide dispersion.0.06 g nano zirconium dioxides are added to 25
In mL 1 g/L graphene oxide solutions, after stirring 2 h, transfer suspension makes it at 150 DEG C into 100 mL water heating kettles
Lower reaction 5-6 h.The solid of acquisition, is washed with deionized 3-4 times, and is dried under conditions of 60 DEG C in vacuum drying chamber
12h is dried, and the product being dried to obtain is redox graphene/nanometer titanium dioxide zirconium composite material.
Embodiment 4：
A kind of redox graphene/nano zirconium dioxide composite adsorption dephosphorization agent, it by following parts by weight raw material system
Into：
Parts by weight of raw materials
Graphene oxide 4
Nano zirconium dioxide 7.
A kind of preparation method of redox graphene/nano zirconium dioxide composite adsorption dephosphorization agent, its step are：
A. graphene oxide preparation method is same as Example 1.
B. the preparation of redox graphene/nanometer titanium dioxide zirconium composite material：The graphite oxide being prepared is dilute super
Sound is scattered in deionized water, prepares 1 g/L graphene oxide dispersion.0.07 g nano zirconium dioxides are added to 20
In mL 1 g/L graphene oxide solutions, after stirring 2 h, transfer suspension makes it at 150 DEG C into 100 mL water heating kettles
Lower reaction 5-6 h.The solid of acquisition, is washed with deionized 3-4 times, and is dried under conditions of 60 DEG C in vacuum drying chamber
12h is dried, and the product being dried to obtain is redox graphene/nanometer titanium dioxide zirconium composite material.
Embodiment 5：
A kind of redox graphene/nano zirconium dioxide composite adsorption dephosphorization agent, it by following parts by weight raw material system
Into：
Parts by weight of raw materials
Graphene oxide 10
Nano zirconium dioxide 11.
A kind of preparation method of redox graphene/nano zirconium dioxide composite adsorption dephosphorization agent, its step are：
A. graphene oxide preparation method is same as Example 1.
B. the preparation of redox graphene/nanometer titanium dioxide zirconium composite material：The graphite oxide being prepared is dilute super
Sound is scattered in deionized water, prepares 1 g/L graphene oxide dispersion.0.11 g nano zirconium dioxides are added to 50
In mL 1 g/L graphene oxide solutions, after stirring 2 h, transfer suspension makes it at 150 DEG C into 100 mL water heating kettles
Lower reaction 5-6 h.The solid of acquisition, is washed with deionized 3-4 times, and is dried under conditions of 60 DEG C in vacuum drying chamber
12h is dried, and the product being dried to obtain is redox graphene/nanometer titanium dioxide zirconium composite material.
Embodiment 6：
A kind of redox graphene/nano zirconium dioxide composite adsorption dephosphorization agent, it by following parts by weight raw material system
Into：
Parts by weight of raw materials
Graphene oxide 15
Nano zirconium dioxide 3.
A kind of preparation method of redox graphene/nano zirconium dioxide composite adsorption dephosphorization agent, its step are：
A. graphene oxide preparation method is same as Example 1.
B. the preparation of redox graphene/nanometer titanium dioxide zirconium composite material：The graphite oxide being prepared is dilute super
Sound is scattered in deionized water, prepares 1 g/L graphene oxide dispersion.0.03 g nano zirconium dioxides are added to 75
In mL 1 g/L graphene oxide solutions, after stirring 2 h, transfer suspension makes it at 150 DEG C into 100 mL water heating kettles
Lower reaction 5-6 h.The solid of acquisition, is washed with deionized 3-4 times, and is dried under conditions of 60 DEG C in vacuum drying chamber
12h is dried, and the product being dried to obtain is redox graphene/nanometer titanium dioxide zirconium composite material.
A kind of redox graphene/nano zirconium dioxide composite adsorption dephosphorization agent, it by following parts by weight raw material system
Into：
| Raw material | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 |
| Graphene oxide | 2 | 2 | 2 | 4 | 10 | 15 |
| Nano zirconium dioxide | 3 | 4 | 6 | 2 | 2 | 2 |
| Amount to（Parts by weight） | 5 | 6 | 8 | 6 | 12 | 17 |
Its preparation method is same as Example 1.
Performance test to the adsorption and dephosphorization agent obtained by embodiment：
Redox graphene/nanometer titanium dioxide zirconium composite material Phosphate Sorption：By redox graphene obtained above/
Nanometer titanium dioxide zirconium powder, weighs 0.2 g and is added to 400 mL concentration and be in 15.0 mg/L solution containing phosphate, fully mixed
Even, 25 DEG C of constant-temperature tables shake 24h, reach adsorption equilibrium.After adsorption equilibrium, composite and phosphorus mixed liquor were centrifuged
Filter, filtrate calculate adsorbance using molybdenum blue colorimetric method measure balance phosphorus concentration.As control, the nanometer two of phase homogenous quantities is taken
Zirconium oxide does identical processing with redox graphene.
Adsorbent adsorption capacity calculation formula Qe=
Co and Ce is respectively phosphorus concentration after initial phosphorus concentration and adsorption equilibrium in formula, mg/L；V is the body of absorption system solution
Product, L；M be adsorbent quality, g；Qe is adsorption capacity, mg/g.
The performance test results are shown in Table 1.
| Adsorption capacity（mg/g） | Nano zirconium dioxide | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 |
| Redox graphene/nanometer titanium dioxide zirconium composite material | 12.34 | 15.67 | 24.56 | 27.29 | 18.22 | 15.10 | 9.23 |
| Redox graphene/nanometer titanium dioxide zirconium composite material（In terms of zirconium dioxide） | 12.34 | 26.12 | 36.84 | 36.38 | 54.66 | 90.6 | 78.46 |
The recycling of redox graphene/nanometer titanium dioxide zirconium composite material：The absorption that will be obtained after centrifugal filtration
The redox graphene of phosphorus/nanometer titanium dioxide zirconium composite material is with 0.1 mol/L NaOH, 0.05 mol/L HCl and goes
Ionized water cleans successively, can retrieve redox graphene/nanometer titanium dioxide zirconium composite material, should by the solid being collected into
For next adsorption experiment.Result of the test shows, the recycling performance of the composite of preparation to phosphorus is good：Passing through 2 times
After recycling, composite reduced by only 5% to the adsorption capacity of phosphorus；25% is reduced by only after 8 recyclings.
Claims (7)
- A kind of 1. redox graphene/application of the nano zirconium dioxide composite adsorption dephosphorization agent in dephosphorization, it is characterised in that The preparation method of the dephosphorization agent comprises the following steps：A. graphene oxide is prepared with graphite powder：The graphite powder for weighing certain part by weight is placed in dry beaker, adds 20- The concentrated sulfuric acids of 40 mL 98%, in 78-82 DEG C of stirred in water bath, sequentially add 5-10 g potassium peroxydisulfates and the oxidations of 5-10 g five two Phosphorus, after persistently stirring 5h, it is cooled to room temperature, adds deionized water dilution, stand overnight, with 0.2 micrometer Millipore filter membrane by powder End filtering, and be washed with deionized, until after solution is changed into neutrality, powder is in 70 DEG C of dryings, the powder transfer being dried to obtain Into beaker, the concentrated sulfuric acids of 240 mL 98% are added, and are stirred under condition of ice bath, are subsequently to added into 20-50g potassium permanganate, After 30-35 DEG C of stirred in water bath 1-3h, diluted with deionized water, lasting stirring, add 30-50 mL30% peroxidating Hydrogen, solution is centrifuged, and washed with watery hydrochloric acid, to remove sulfate ion, detected with barium nitrate solution, except desulfuration It is washed with deionized after acid ion until washing lotion is neutrality, obtained product is dried at 68-72 DEG C, that is, obtains oxygen Graphite alkene solid powder；B. the preparation of redox graphene/nanometer titanium dioxide zirconium composite material：By the graphene oxide being prepared ultrasound point The graphene oxide dispersion for preparing 1 g/L in deionized water is dissipated, by the 0.01-1 g nano zirconium dioxide through pre-treatment It is added in the 1g/L graphene oxide solutions of certain volume, after stirring 1-3h, shifts suspension into water heating kettle, and 5-6 h are reacted under 148-152 DEG C of environment, the solid of acquisition is washed with deionized, and is done under conditions of 58-62 DEG C in vacuum Dry 11-13h in dry case to be dried, the product being dried to obtain is redox graphene/nanometer titanium dioxide zirconium composite material；C. redox graphene/nanometer titanium dioxide zirconium composite material Phosphate Sorption：By redox graphene obtained above/ Nanometer titanium dioxide zirconium powder, weigh 0.1-1g be added to certain volume concentration be 1-15 mg/L solution containing phosphate in, fully Mix, constant-temperature table concussion 22-26h, reach adsorption equilibrium, after adsorption equilibrium, by composite and phosphorus mixed liquor centrifugal filtration, Filtrate calculates adsorbance using molybdenum blue colorimetric method measure balance phosphorus concentration；Wherein, before described graphene oxide and nano zirconium dioxide are compound, the first 550 DEG C of calcination processing 1-3h of nano zirconium dioxide To remove the impurity on surface；The parts by weight for preparing the raw material of redox graphene/nano zirconium dioxide are as follows：Graphene oxide 1-40 partsNano zirconium dioxide 1-30 parts.
- 2. application according to claim 1, it is characterised in that prepare the original of redox graphene/nano zirconium dioxide The parts by weight of material are as follows：Graphene oxide 2-30 partsNano zirconium dioxide 2-20 parts.
- 3. application according to claim 1, it is characterised in that prepare the original of redox graphene/nano zirconium dioxide The parts by weight of material are as follows：Graphene oxide 3-20 partsNano zirconium dioxide 3-15 parts.
- 4. application according to claim 1, it is characterised in that prepare the original of redox graphene/nano zirconium dioxide The parts by weight of material are as follows：Graphene oxide 4-12 partsNano zirconium dioxide 4-10 parts.
- 5. application according to claim 1, it is characterised in that prepare the original of redox graphene/nano zirconium dioxide The parts by weight of material are as follows：10 parts of graphene oxide2 parts of nano zirconium dioxide.
- 6. application according to claim 1, it is characterised in that prepare the original of redox graphene/nano zirconium dioxide The parts by weight of material are as follows：2 parts of graphene oxide2 parts of nano zirconium dioxide.
- 7. application according to claim 1, it is characterised in that prepare the original of redox graphene/nano zirconium dioxide The parts by weight of material are as follows：3 parts of graphene oxide4 parts of nano zirconium dioxide.
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| CN100519475C (en) * | 2003-04-02 | 2009-07-29 | 珠海粤科京华电子陶瓷有限公司 | Method of preparing zirconium oxide ceramic by curtain coating method and product obtained by using the method |
| CN102910700B (en) * | 2012-11-14 | 2014-10-22 | 南京大学 | Method for removing phosphate in water through absorption of graphite oxide modified by zirconia |
| CN102941063B (en) * | 2012-12-12 | 2014-07-02 | 南京大学 | Method for adsorbing and removing phosphates from water body by using zirconium oxide modified carbon nano tubes |
| CN103861559A (en) * | 2014-03-12 | 2014-06-18 | 陕西科技大学 | Zirconia-modified graphene and method for removing fluorine ions in water |
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